Identification and quantification of carotenoids including geometrical isomers in fruit and vegetable juices by liquid chromatography with ultraviolet-diode array detection

A method was established for the identification and quantification of carotenoids including geometrical isomers in fruit and vegetable juices by liquid chromatography with an ultraviolet-diode array detector, using a C(18) Vydac 201TP54 column. The mobile phase used was the ternary methanol mixture (0.1 M ammonium acetate), tert-butyl methyl ether and water, in a concentration gradient, and a temperature gradient was applied. Retinol palmitate was added as an internal standard. An extraction process (ethanol/hexane, 4:3, v/v) was performed, followed by saponification with diethyl ether/methanolic KOH (0.1%, w/v, BHT) (1:1, v/v) for 0.5 h at room temperature. Seventeen different (cis and trans) carotenoids were identified by UV-vis spectra and retention times in HPLC in the juices analyzed. The analytic parameters show that the method proposed is sensitive, reliable, accurate, and reproducible.     

Assessing soil erosion and control factors by the radiometric technique in the Boussouab catchment,Eastern Rif,Morocco

In the Eastern Rif of N Morocco, soil conservation is seriously threatened by water erosion. Large areas of soil have reached an irreversible state of degradation. In this study, the ¹³⁷Cs technique was used to quantify erosion rates and identify the main factors involved in the erosion process based on a representative catchment of the Eastern Rif. To estimate erosion rates in terms of the main factors affecting soil losses, samples were collected taking into account the lithology, slope and land use along six selected transects within the Boussouab catchment. The transects were representative of the main land uses and physiographic characteristics of that Rif sector. The reference inventory for the area was established at a stable, well preserved, matorral site (value of 4250 Bq m^− 2). All the sampling sites were eroded and ¹³⁷Cs inventories varied widely (between 245 and 3670 Bq m^− 2). The effective soil losses were also highly variable (between 5.1 and 48.8 t ha^− 1 yr^− 1). Soil losses varied with land use. The lowest average values were on matorral and fallow land (10.5 and 15.2 t ha^− 1 yr^− 1, respectively) but much higher with alfa vegetation or cereal crops (31.6 and 27.3, respectively). The highest erosion rate was on a badland transect at the more eroded part of the catchment, with rates exceeding 40 t ha^− 1 yr^− 1 and reaching a maximum of 48.8 t ha^− 1 yr^− 1.The average soil losses increased by more than 100% when the slope increased from 10° (17.7 t ha^− 1 yr^− 1) to 25° (40. 8 t ha^− 1 yr^− 1). Similar results were obtained when comparing erosion rates in soils that were covered by matorral with respect to those under cultivation. Lithology was also a key factor affecting soil loss. Soils on marls were more erodible and the average erosion rates reached 29.36 t ha^− 1 yr^− 1, which was twice as high as soils on the glacis and old fluvial terraces (average rates of 14.98 t ha^− 1 yr^− 1). The radiometric approach was very useful to quantify erosion rates and to examine the pattern of soil movement. The analysis of main erosion factors can help to promote rational soil use and establish conservation strategies in the study area.     

Diterpenes from Salvia broussonetii transformed roots and their insecticidal activity

The new diterpenes brussonol (1) and iguestol (6alpha,11-dihydroxy-12-methoxy-abieta-8,11,13-triene) (2) with an icetexane and a dehydroabietane skeleton, respectively, have been isolated from hairy root cultures of Salvia broussonetii. Other previously known diterpenes, 7-oxodehydroabietane, 11-hydroxy-12-methoxyabietatriene, taxodione, inuroyleanol, ferruginol, deoxocarnosol 12-methyl ether, cryptojaponol, pisiferal, sugiol, isomanool, 14-deoxycoleon U, 6alpha-hydroxydemethylcryptojaponol, demethylsalvicanol, and demethylcryptojaponol, were also obtained from these roots. The insect antifeedant and toxic effects of several of these compounds were investigated against the insect pests Spodoptera littoralis and Leptinotarsa decemlineata. Additionally, their comparative cytotoxic effects were tested on insect Sf9 and mammalian CHO cells. Demethylsalvicanol (4) was a moderate antifeedant to L. decemlineata, whereas brussonol (1) was inactive. 14-Deoxycoleon U (15) was the strongest antifeedant, whereas demethylcryptojaponol (11) was toxic to this insect. None of these compounds had antifeedant or negative effects on S. littoralis ingestion or weight gains after oral administration. Demethylcryptojaponol (11) was cytotoxic to mammalian CHO and insect Sf9 cell lines, followed by the icetexane derivative brussonol (1), with moderate cytotoxicity in both cases. The remainder of the test compounds showed a strong selective cytotoxicty to insect Sf9 cells, with demethylsalvicanol (4) being the most active.     

Interaction of contaminated sediment from a salt marsh with estuarine water: evaluation by leaching and ecotoxicity assays and salts from leachate evaporation

Purpose

Wastes from a former Portuguese steel plant were deposited between 1961 and 2001 on the riverbank of a tributary of the Tagus River creating a landfill connected to the river, posing a potential contamination risk to the Tagus estuary ecosystem. This study aims to assess the transfer of chemical elements from contaminated sediments to the estuarine water from cycles of sediment leaching so as to evaluate the ecotoxicity of the leachates, and to analyze the solid phases crystallized from those leachates.

Materials and methods

Landfill sediment and estuarine water samples were collected during low tide. Sediment samples were analyzed for pH, electric conductivity (EC), C_org, NPK, and iron oxides. Leaching assays (four replicates) were done using estuarine water (200 cm³/replicate) and 1.5 kg of sediment per reactor. Each reactor was submitted to four leaching processes (0, 28, 49, and 77 days). The sediment was kept moist between leaching processes. Sediment (total (acid digestion) and available fraction (diluted organic acid extraction-Rhizo)) elemental concentrations were determined by inductively coupled plasma–instrumental neutron activation analysis (ICP/INAA). Leachates, and estuarine and sediment pore waters were analyzed for metals/metalloids by ICP/mass spectrometry (MS) and carbonates/sulfate/chloride by standard methodologies. Ecotoxicity assays were performed in leachates and estuarine and pore waters using Artemia franciscana and Brachionus plicatillis. Aliquots of the leachates were evaporated to complete dryness (23–25 °C) and crystals analyzed by X-ray powder diffraction (XRD).

Results and discussion

Sediment with pH?=?8 and high EC and C_org was contaminated with As, Cd, Cr, Cu, Pb, and Zn. The element concentrations in the available fraction of the sediment were low compared to the sediment total concentrations (<1 % for Rhizo extraction). The concentrations of potentially hazardous elements in the estuarine water were relatively low, except for Cd. Concentrations of hazardous elements in the leachates were very low. Calcium, K, Mg, Na, and chloride concentrations were high but did not vary significantly among the four leaching experiments. Total concentrations of carbonate were much higher in leachates than in estuarine water. Both estuarine water and leachates showed negligible toxicity. Crystals identified in the solids obtained from the leachates by evaporation were halite, anhydrite, epsomite, dolomite, and polyhalite.

Conclusions

The sediment showed the capacity to retain the majority of the potentially hazardous chemical elements. Remobilization of chemical elements from sediment by leaching was essentially negligible. The variation of total concentrations of Ca, carbonate, and sulfate in leachates indicates that the sediment contained reactive sulfides. Due to its composition, the sediment seems to be a dynamic system of pollution control, which should not be disturbed.

     

Essential oils from plants and in vitro shoots of Hypericum androsaemum L

The essential oil yields obtained by hydrodistillation of the aerial parts of Hypericum androsaemum cultivated plants varied from 0.94 to 4.09 mg/g of biomass dry weight, depending of the harvest time. The respective analyses performed by gas chromatography and gas chromatography-mass spectrometry revealed more than 80 compounds, 72 of which were identified. Most of the compounds were sesquiterpene hydrocarbons, which, depending of the harvest time, corresponded to 43-78% of the total essential oil. The other compounds were distributed as monoterpene hydrocarbons, oxygen-containing sesquiterpenes, n-alkanes, 1-alkenes, and oxygen-containing monoterpenes, these being a minor group. In H. androsaemum in vitro shoots, sesquiterpene hydrocarbons represented >80% of the respective essential oil. Differences in the essential oil composition were found depending on the harvest time and origin, in vivo versus in vitro, of the plant material. The essential oil sampled in November was characterized by the highest levels of sesquiterpene hydrocarbons and a high number of n-alkanes and 1-alkenes, from C(18) to C(28), whereas that sampled in June of the following year showed the highest levels of n-nonane and 1-octene as well as monoterpene hydrocarbons, the second most representative group.     

Dissolved and Particulate Heavy Metals in the Salado River (Santa FE, Argentina)

The objective of this work is to analyze Fe, Mn, Cr, Cd, Cu, Pb, and Zn distributions in the water column in terms of total, dissolved, and particulate concentrations in the Salado River (Santa Fe – Argentina); their relationship with total, dissolved and suspended solids; and the impact of two pollution sources on the watercourse: a stream that collects domestic and industrial wastewater discharges of the region and a direct discharge that releases urban and industrial effluents to the river. Water samples obtained from 5 surveys were analyzed. The Salado River transported a load of heavy metals that ranged from 700 g/s to 2200 g/s of Fe, 20 g/s to 60 g/s of Mn and 1 g/s to 3 g/s of Cr. Results show that most metals were found in particulate form, that the metal input from the direct discharge may be significant at low water levels, whereas a lesser impact was produced by the stream, and that both pollution sources were negligible at high water levels.     

Chemical characterization of the aroma of Grenache rosé wines: aroma extract dilution analysis,quantitative determination,and sensory reconstitution studies

The aroma of a Grenache rosé wine from Calatayud (Zaragoza, Spain) has been elucidated following a strategy consisting of an aroma extract dilution analysis (AEDA), followed by the quantitative analysis of the main odorants and the determination of odor activities values (OAVs) and, finally, by a series of reconstitution and omission tests with synthetic aroma models. Thirty-eight aroma compounds were found in the AEDA study, 35 of which were identified. Twenty-one compounds were at concentrations higher than their corresponding odor thresholds. An aroma model prepared by mixing the 24 compounds with OAV > 0.5 in a synthetic wine showed a high qualitative similarity with the aroma of the rosé wine. The addition of compounds with OAV < 0.5 did not improve the model, whereas the aroma of a model containing only odorants with OAV > 10 was very different from that of the wine. Omission tests revealed that the most important odorant of this Grenache rosé wine was 3-mercapto-1-hexanol, with a deep impact on the wine fruity and citric notes. The synergic action of Furaneol and homofuraneol also had an important impact on wine aroma, particularly in its fruity and caramel notes. The omission of beta-damascenone, which had the second highest OAV, caused only a slight decrease on the intensity of the aroma model. Still weaker was the sensory effect caused by the omission of 10 other compounds, such as fatty acids and their ethyl esters, isoamyl acetate, and higher alcohols.     

Interactive responses to water deficits and crop load in olive (Olea europaea L., cv. Morisca). II: Water use, fruit and oil yield

To understand the relations between water use and yield in response to crop load, two experiments were conducted in olive (cv. Morisca), during six consecutive years (2002-2007) in an experimental orchard located in Badajoz, Southwest Spain. Experiment 1, assessed the responses during the early years of the orchard (2002-2004) using four irrigation treatments that applied fractions of the estimated crop evapotranspiration (ET_c) (125%, 100%, 75% and 0%) and three crop load levels (100%, 50% and 0% of fruit removal, termed Off, Medium and On treatments). Experiment 2 assessed the response of more mature trees (2005-2007) to three irrigation treatments (115%, 100%, and 60% of ET_c) and the natural crop load which were Off, On, and Medium in 2005, 2006 and 2007, respectively. Yield was reduced by water deficits and so did the estimated tree transpiration which was linearly related to yield (y = 1.2302x − 21.15, R² = 0.8864), showing the high sensitivity of cultivar Morisca to water deficits. The relations between fruit number and fruit weight showed that high crop loads had lower fruit weights and oil yield, a decrease that was more pronounced as water deficits increased. The yield response to water supply in the control and excess treatments, and the observations on the water relations of these two treatments suggest that the calculations made using the FAO method (Doorenbos and Pruit, 1974) with the crop coefficient proposed by Pastor et al. (1998) and the reduction coefficient (Fereres et al., 1982) to apply 100% of ET_c in the control treatment, underestimated the ET_c of the orchard. The results indicate that, although the absence of fruits lead to reduced water use as compared to situations of medium and high crop loads, canopy size was much more determinant of orchard water requirements than crop load.     

Monitoring of blood vessels and tissues by a population of monocytes with patrolling behavior

The cellular immune response to tissue damage and infection requires the recruitment of blood leukocytes. This process is mediated through a classical multistep mechanism, which involves transient rolling on the endothelium and recognition of inflammation followed by extravasation. We have shown, by direct examination of blood monocyte functions in vivo, that a subset of monocytes patrols healthy tissues through long-range crawling on the resting endothelium. This patrolling behavior depended on the integrin LFA-1 and the chemokine receptor CX(3)CR1 and was required for rapid tissue invasion at the site of an infection by this "resident" monocyte population, which initiated an early immune response and differentiated into macrophages.